WO2014119166A1 - Transducteur souple - Google Patents

Transducteur souple Download PDF

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Publication number
WO2014119166A1
WO2014119166A1 PCT/JP2013/083911 JP2013083911W WO2014119166A1 WO 2014119166 A1 WO2014119166 A1 WO 2014119166A1 JP 2013083911 W JP2013083911 W JP 2013083911W WO 2014119166 A1 WO2014119166 A1 WO 2014119166A1
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WIPO (PCT)
Prior art keywords
semiconductor
dielectric layer
containing layer
layer
type semiconductor
Prior art date
Application number
PCT/JP2013/083911
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English (en)
Japanese (ja)
Inventor
高橋　渉
吉川　均
成亮 高松
Original Assignee
東海ゴム工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by 東海ゴム工業株式会社 filed Critical 東海ゴム工業株式会社
Priority to JP2014528747A priority Critical patent/JP5633769B1/ja
Publication of WO2014119166A1 publication Critical patent/WO2014119166A1/fr
Priority to US14/674,231 priority patent/US20150202656A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B06—GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS IN GENERAL
    • B06B—METHODS OR APPARATUS FOR GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS OF INFRASONIC, SONIC, OR ULTRASONIC FREQUENCY, e.g. FOR PERFORMING MECHANICAL WORK IN GENERAL
    • B06B1/00—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency
    • B06B1/02—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy
    • B06B1/06—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy operating with piezoelectric effect or with electrostriction
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R19/00—Electrostatic transducers
    • H04R19/005—Electrostatic transducers using semiconductor materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/20—Piezoelectric or electrostrictive devices with electrical input and mechanical output, e.g. functioning as actuators or vibrators
    • H10N30/206—Piezoelectric or electrostrictive devices with electrical input and mechanical output, e.g. functioning as actuators or vibrators using only longitudinal or thickness displacement, e.g. d33 or d31 type devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/30—Piezoelectric or electrostrictive devices with mechanical input and electrical output, e.g. functioning as generators or sensors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/857—Macromolecular compositions
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R19/00—Electrostatic transducers
    • H04R19/02—Loudspeakers
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R19/00—Electrostatic transducers
    • H04R19/04—Microphones
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/80—Constructional details
    • H10K10/82—Electrodes

Definitions

  • the present invention relates to a flexible transducer using an elastomeric material.
  • an actuator that converts mechanical energy and electrical energy, a sensor, a power generation element, or a speaker that converts acoustic energy to electrical energy, a microphone, and the like are known.
  • Polymeric materials such as dielectric elastomers are useful for constructing a flexible, compact and lightweight transducer.
  • a flexible transducer can be configured by arranging a pair of electrodes on both sides in the thickness direction of a sheet-like dielectric layer made of dielectric elastomer.
  • the charge between the electrodes can generate a force, and the charge generated by the deformation can be detected or generated.
  • the dielectric layer sandwiched between the electrodes is compressed from the thickness direction, and the thickness of the dielectric layer becomes thinner.
  • the dielectric layer elongates in a direction parallel to the electrode surface.
  • the voltage applied between the electrodes is reduced, the electrostatic attraction between the electrodes is reduced.
  • the force and displacement output from the actuator are determined by the magnitude of the applied voltage and the relative permittivity of the dielectric layer. That is, as the applied voltage is larger and the relative permittivity of the dielectric layer is larger, the generated force and the displacement amount of the actuator are larger. For this reason, as a material of the dielectric layer, silicone rubber having high dielectric breakdown resistance, acrylic rubber having a large dielectric constant, nitrile rubber, or the like is used (see, for example, Patent Document 1).
  • the dielectric layer made of silicone rubber is resistant to dielectric breakdown even when a large voltage is applied.
  • the polarity of silicone rubber is small. That is, the dielectric constant of silicone rubber is small.
  • the actuator is configured using a dielectric layer made of silicone rubber, the electrostatic attraction to the applied voltage is small. Therefore, due to the practical voltage, desired force and displacement can not be obtained.
  • the dielectric constant of acrylic rubber and nitrile rubber is larger than the dielectric constant of silicone rubber.
  • the electrostatic attractive force with respect to the applied voltage is larger than that when silicone rubber is used.
  • the electrical resistance of acrylic rubber or the like is smaller than that of silicone rubber. Therefore, dielectric layers made of acrylic rubber or the like are prone to dielectric breakdown.
  • a current easily flows in the dielectric layer at the time of voltage application (because the so-called leakage current is large)
  • charges are not easily accumulated at the interface between the dielectric layer and the electrode. Therefore, although the relative dielectric constant is large, the electrostatic attraction becomes small, and a sufficient amount of force and displacement can not be obtained.
  • an elastomer alone it is difficult to realize a dielectric layer that satisfies both electrostatic attraction and resistance to dielectric breakdown.
  • the dielectric constant of the dielectric layer needs to be large. At the same time, high insulation is required to hold the charge. Also, in order to improve the performance of the power generation element and the speaker, it is essential to be able to hold a large amount of charge. However, it is difficult for the elastomer alone to simultaneously achieve a large relative dielectric constant and high insulation.
  • the present invention has been made in view of such circumstances, and it is an object of the present invention to provide a flexible transducer which is provided with a dielectric layer containing an elastomer, has high resistance to dielectric breakdown, and can output a large force. Do.
  • the flexible transducer of the present invention comprises a dielectric layer having a semiconductor-containing layer comprising an elastomer and at least one of an inorganic semiconductor and an organic semiconductor, and a pair of electrodes disposed across the dielectric layer and containing a binder and a conductive material. And.
  • the dielectric layer interposed between the pair of electrodes includes a semiconductor including an elastomer and at least one of an inorganic semiconductor and an organic semiconductor (hereinafter collectively referred to as “semiconductor”). With layers.
  • the semiconductors include n-type semiconductors having free electrons (charged particles having a negative charge) and p-type semiconductors having holes (charged particles having a positive charge). For example, when a voltage is applied to an n-type semiconductor-containing layer containing an n-type semiconductor, free electrons move to generate charge bias inside the n-type semiconductor.
  • the holes move to cause charge bias inside the p-type semiconductor.
  • the occurrence of polarization inside the semiconductor increases the relative dielectric constant.
  • free electrons and holes (carriers) become a barrier due to the insulating elastomer which is a base material, and hardly flow as a current in the dielectric layer. Therefore, the semiconductor-containing layer has a large dielectric constant but is less likely to cause dielectric breakdown.
  • the dielectric layer may be composed of only the semiconductor-containing layer (which may be a single layer or a plurality of layers), but may have other layers in addition to the semiconductor-containing layer.
  • a high resistance layer having high electric resistance can be stacked on the semiconductor-containing layer.
  • the electrical resistance of the high resistance layer adjacent to the semiconductor-containing layer is large.
  • a large amount of charge is stored at the interface between the semiconductor-containing layer and the high resistance layer. Therefore, a large electrostatic attractive force is generated to compress the semiconductor-containing layer and the high resistance layer, and a large force can be output.
  • the flexible transducer of the present invention by having the semiconductor-containing layer as the dielectric layer, a large electrostatic attraction can be generated in the dielectric layer. Also, the dielectric breakdown strength of the dielectric layer is large. Thus, according to the flexible transducer of the present invention, a large voltage can be applied to output a large force. In addition, when the flexible transducer of the present invention is used as a capacitive sensor, the resolution of displacement is high because the capacitance of the semiconductor-containing layer is large.
  • an elastomer may be blended with an ionic component.
  • molecules of the ion component are inverted and polarized. Thereby, many charges can be generated in the dielectric layer.
  • ion polarization requires inversion of the ion molecule itself.
  • the higher the frequency the speed at which the substance inverts can not keep up with the frequency. Therefore, when a high frequency AC voltage is applied, the polarization can not follow the change in voltage. Therefore, it is up to a low frequency of about 10 Hz that the effect of improving the relative dielectric constant can be obtained by blending the ion component.
  • the charge density is increased by the carrier (hole or free electron) of the semiconductor. Since the movement of carriers does not involve inversion of substances like ion polarization, the effect of improving the relative dielectric constant by polarization can be obtained even if the frequency of the applied voltage is high.
  • the flexible transducer of the present invention is also suitable for applications where high frequency alternating voltage is applied.
  • blended the ion component and the high resistance layer mentioned above are laminated
  • the semiconductor-containing layer of the present invention carriers of the semiconductor move by applying a voltage, but the semiconductor itself (fixed charge) does not move. Therefore, even if the semiconductor-containing layer and the high resistance layer are stacked, there is no change with time due to the movement of the semiconductor itself. For this reason, the reduction in the electrical resistance of the high resistance layer and the dielectric breakdown are unlikely to occur.
  • Patent Document 2 discloses a thermoelectric power generation module in which an n-type thermoelectric semiconductor substrate and a p-type thermoelectric semiconductor substrate are joined.
  • the thermoelectric power generation module described in Patent Document 2 uses the Peltier effect or the Seebeck effect, and is different from the flexible transducer of the present invention utilizing the electrostrictive effect.
  • the n-type thermoelectric semiconductor substrate described in Patent Document 2 is one in which n-type thermoelectric semiconductor particles are blended in a conductive resin having a volume resistivity of 10 -4 to 10 3 ⁇ ⁇ cm, which is a mixture of synthetic rubber and conductive particles. It is.
  • the p-type thermoelectric semiconductor substrate is obtained by blending p-type thermoelectric semiconductor particles in the above-mentioned conductive plastic.
  • thermoelectric semiconductor substrate and the p-type thermoelectric semiconductor substrate also differ from the semiconductor-containing layer of the present invention in that the conductivity is imparted by the conductive particles.
  • Patent Document 3 discloses a composition having an insulating binder, conductive particles, and semiconductor particles. The composition described in Patent Document 3 is used to protect an electronic component against electrical overload transients, and differs from the semiconductor-containing layer of the present invention in that the conductivity is imparted by conductive particles.
  • Patent Document 4 discloses an electrostrictive actuator including an elastic body, a semiconductive layer, and a pair of electrodes. The semiconductive layer is different from the semiconductor-containing layer of the present invention in that the semiconductive layer contains a conductive substance such as carbon powder and does not contain a semiconductor.
  • FIG. 6 is a cross-sectional view taken along the line VI-VI of FIG. 5; It is a cross-sectional schematic diagram of the electric power generation element which is 6th embodiment of the transducer of this invention, Comprising: (a) shows at the time of expansion
  • FIG. 11 is a cross-sectional view taken along line XI-XI of FIG. It is a top view of the actuator used for evaluation experiment. It is a XIII-XIII sectional view of FIG.
  • Transducer 10: Dielectric layer, 11a, 11b: Electrode, 12: n-type semiconductor containing layer, 13: p-type semiconductor containing layer, 14: high resistance layer.
  • actuator 50: dielectric layer, 51a, 51b: electrode, 52: upper chuck, 53: lower chuck.
  • the flexible transducer of the present invention comprises a dielectric layer and a pair of electrodes disposed across the dielectric layer.
  • the dielectric layer is disposed between the pair of electrodes.
  • the dielectric layer may be a single layer or two or more layers as long as it has a semiconductor-containing layer.
  • a configuration example of the dielectric layer will be described by taking the case of using the flexible transducer of the present invention as an actuator as an example.
  • the flexible transducer of the present invention is used as a speaker, a power generation element, a sensor or the like, the same configuration as described below can be adopted.
  • FIG. 1 shows a schematic cross-sectional view of the transducer of the present embodiment.
  • the transducer 1 includes a dielectric layer 10 and a pair of electrodes 11 a and 11 b.
  • the dielectric layer 10 is composed of an n-type semiconductor containing layer 12.
  • the n-type semiconductor-containing layer 12 contains nitrile rubber and P-doped SnO 2 particles of n-type semiconductor inorganic particles. Nitrile rubber is included in the elastomer of the present invention.
  • the electrode 11 a is a plus electrode and is disposed on the upper surface of the n-type semiconductor-containing layer 12.
  • the electrode 11 b is a negative electrode, and is disposed on the lower surface of the n-type semiconductor-containing layer 12.
  • the applied voltage can be increased to obtain a large amount of force and displacement. Moreover, the transducer 1 is excellent in durability.
  • the transducer 1 includes a dielectric layer 10 and a pair of electrodes 11 a and 11 b.
  • the dielectric layer 10 is composed of an n-type semiconductor-containing layer 12 and a p-type semiconductor-containing layer 13.
  • the n-type semiconductor-containing layer 12 is stacked on the top surface of the p-type semiconductor-containing layer 13.
  • the p-type semiconductor-containing layer 13 contains nitrile rubber and nickel oxide particles of p-type semiconductor inorganic particles.
  • the electrode 11 a is a plus electrode and is disposed on the upper surface of the n-type semiconductor-containing layer 12.
  • the electrode 11 b is a minus electrode, and is disposed on the lower surface of the p-type semiconductor-containing layer 13.
  • the transducer 1 includes a dielectric layer 10 and a pair of electrodes 11 a and 11 b.
  • the dielectric layer 10 is composed of an n-type semiconductor containing layer 12 and a high resistance layer 14.
  • the n-type semiconductor-containing layer 12 is stacked on the upper surface of the high resistance layer 14.
  • the high resistance layer 14 contains nitrile rubber and TiO 2 of insulating particles.
  • the volume resistivity of the high resistance layer 14 is 8 ⁇ 10 13 ⁇ ⁇ cm.
  • the electrode 11 a is a plus electrode and is disposed on the upper surface of the n-type semiconductor-containing layer 12.
  • the electrode 11 b is a negative electrode and is disposed on the lower surface of the high resistance layer 14.
  • FIG. 4 shows a schematic cross-sectional view of the transducer of this embodiment. About the member corresponding to FIG. 2, FIG. 3, it shows with the same code
  • the transducer 1 includes a dielectric layer 10 and a pair of electrodes 11a and 11b.
  • the dielectric layer 10 is composed of an n-type semiconductor-containing layer 12, a p-type semiconductor-containing layer 13, and a high resistance layer 14.
  • the high resistance layer 14 is interposed between the n-type semiconductor containing layer 12 and the p-type semiconductor containing layer 13.
  • the electrode 11 a is a plus electrode and is disposed on the upper surface of the n-type semiconductor-containing layer 12.
  • the electrode 11 b is a minus electrode, and is disposed on the lower surface of the p-type semiconductor-containing layer 13.
  • polarization occurs in the n-type semiconductor inorganic particles in the n-type semiconductor-containing layer 12. Also, in the p-type semiconductor-containing layer 13, polarization occurs inside the p-type semiconductor inorganic particles. Thereby, the charge density of the n-type semiconductor-containing layer 12 and the p-type semiconductor-containing layer 13 is increased, and the relative dielectric constant is increased. Further, when the applied voltage is further increased, part of free electrons of the n-type semiconductor inorganic particles move into the nitrile rubber of the base material. On the other hand, the n-type semiconductor inorganic particles themselves with positive fixed charge hardly move.
  • the electrical resistance of the high resistance layer 14 is large. Therefore, a large amount of charge is stored at the interface between the n-type semiconductor containing layer 12 and the high resistance layer 14 and at the interface between the p-type semiconductor containing layer 13 and the high resistance layer 14. Therefore, a large electrostatic attraction is generated between the pair of electrodes 11 a and 11 b so as to compress the n-type semiconductor containing layer 12, the high resistance layer 14, and the p-type semiconductor containing layer 13.
  • the semiconductor-containing layer includes an elastomer and at least one of an inorganic semiconductor and an organic semiconductor.
  • Elastomers include crosslinked rubbers and thermoplastic elastomers. These may be used alone or in combination of two or more.
  • the elastomer may be selected appropriately according to the performance required for the transducer. For example, an elastomer having a large polarity, that is, a large dielectric constant, is desirable from the viewpoint of increasing the electrostatic attraction generated when a voltage is applied. Specifically, one having a relative dielectric constant of 2.8 or more (measurement frequency 100 Hz) is preferable.
  • nitrile rubber NBR
  • hydrogenated nitrile rubber H-NBR
  • acrylic rubber natural rubber
  • isoprene rubber ethylene-vinyl acetate copolymer
  • ethylene-vinyl acetate-acrylic examples thereof include acid ester copolymers, butyl rubber, styrene-butadiene rubber, fluororubber, epichlorohydrin rubber, chloroprene rubber, chlorinated polyethylene, chlorosulfonated polyethylene, and urethane rubber.
  • an elastomer modified by introducing a functional group may be used.
  • modified elastomer for example, carboxyl group-modified nitrile rubber (X-NBR), carboxyl group-modified hydrogenated nitrile rubber (XH-NBR) and the like are preferable.
  • X-NBR and XH-NBR those having an acrylonitrile content (an amount of bonded AN) of 33% by mass or more are desirable.
  • the bonded AN amount is a mass ratio of acrylonitrile when the total mass of the rubber is 100% by mass.
  • an elastomer having a large electric resistance is desirable in that it is difficult to cause dielectric breakdown when a voltage is applied.
  • the elastomer having a large electric resistance include silicone rubber and ethylene-propylene-diene copolymer.
  • thermoplastic elastomer since a thermoplastic elastomer does not use a crosslinking agent, it is hard to contain an impurity and it is suitable.
  • thermoplastic elastomers styrene-based (SBS, SEBS, SEPS), olefin-based (TPO), polyvinyl chloride-based (TPVC), urethane-based (TPU), ester-based (TPEE), amide-based (TPAE), and co-polymers thereof Polymers and blends may be mentioned.
  • the inorganic semiconductor desirably contains particles of a p-type or n-type semiconductor made of an inorganic substance.
  • the p-type or n-type semiconductor may be a material in which an intrinsic semiconductor is slightly doped with a predetermined element, or a material showing p-type or n-type such as oxide and chalcogenide.
  • Chalcogenides include sulfides, selenides, and telluride. Among these, oxides or sulfides, in particular metal oxides or metal sulfides are preferable from the viewpoint of stability and safety.
  • metal oxides exhibiting p-type and metal sulfides include compounds containing nickel, compounds containing monovalent copper, and compounds containing cobalt. Specifically, nickel oxide, copper oxide, complex oxide of cobalt and sodium (for example, Na x CoO 4 ), and the like can be mentioned. Note that the metal oxide and the metal sulfide may be those in which an element is partially substituted or those in which a predetermined element is slightly doped.
  • n-type metal oxides include zinc oxide, titanium oxide, zirconium oxide, indium oxide, bismuth oxide, vanadium oxide, tantalum oxide, tantalum oxide, niobium oxide, tungsten oxide, tin oxide, tin oxide, iron oxide, potassium tantalate, barium titanate And calcium titanate and strontium titanate.
  • Metal sulfides include cadmium sulfide, zinc sulfide, and indium sulfide. Note that the metal oxide and the metal sulfide may be those in which an element is partially substituted or those in which a predetermined element is slightly doped.
  • metal oxides and metal sulfides those in which an element is partially substituted or those in which a predetermined amount of a predetermined element is doped Is desirable.
  • Those doped with Al, those doped with Al and Ga in zinc oxide, and those doped with Sn in indium oxide are preferable.
  • oxygen deficiency may be generated by reduction annealing or the like to increase the carrier concentration.
  • the doping amount of the element may be appropriately determined because the optimum value varies depending on the base particle to be doped.
  • the doping amount is desirably 0.01 mol% or more and 20 mol% or less. If the doping amount is less than 0.01 mol%, the effect of improving the relative dielectric constant is small, and if it exceeds 20 mol%, the relative dielectric constant is rather reduced. More preferably, it is 0.5 mol% or more and 10 mol% or less.
  • the semiconductor particles contained in the semiconductor-containing layer may be one kind or two or more kinds.
  • semiconductor particles commercially available powders may be used, or those synthesized by solid phase synthesis method, supercritical hydrothermal synthesis method, hydrothermal synthesis method, sol-gel method, oxalic acid method or the like may be used.
  • solid phase synthesis it is easy to control the doping amount, it is easy to obtain particles of any doping amount.
  • crystallinity of the resulting particles is also enhanced.
  • a hydrothermal synthesis method, a supercritical hydrothermal synthesis method, or a sol-gel method nano-sized particles with high crystallinity can be obtained.
  • the electrical resistance of the semiconductor-containing layer is increased, and the semiconductor-containing layer is less likely to cause dielectric breakdown.
  • the semiconductor-containing layer can be thinned by using nano-sized particles. By thinning the semiconductor-containing layer and hence the dielectric layer, the volumetric energy density of the transducer can be increased. In addition, power saving can be achieved by reducing the applied voltage.
  • the semiconductor particles are desirably present in mono-dispersed state in the elastomer. If the semiconductor particles are present in a state of being agglomerated in the elastomer, the insulating properties of the agglomerated part are impaired, and the insulating properties of the entire semiconductor-containing layer are lowered. This lowers the dielectric breakdown strength of the dielectric layer.
  • the semiconductor particles may be subjected to known surface treatment depending on the type of elastomer. Under the present circumstances, as a surface treatment agent, what can be covalently bonded with both a semiconductor particle and an elastomer is desirable.
  • the affinity between the semiconductor particles and the elastomer is increased by covalent bonding, microvoids are less likely to be generated, and the semiconductor particles are less likely to be separated from the elastomer. Thereby, the dielectric breakdown strength of the semiconductor-containing layer is increased.
  • semiconductor particles synthesized by the sol-gel method have many hydroxyl groups on the particle surface. For this reason, even if it does not surface-treat, it is easy to carry out covalent bond with an elastomer. Therefore, semiconductor particles synthesized by the sol-gel method are suitable for increasing the dielectric breakdown strength of the semiconductor-containing layer.
  • the semiconductor particles preferably have high carrier density. If the carrier density of the semiconductor particles is high, the charge density of the semiconductor-containing layer can be increased even if the blending amount to the elastomer is small. When the compounding amount of the semiconductor particles is small, the flexibility of the semiconductor-containing layer is improved. In addition, since the distance between the semiconductor particles in the elastomer becomes large, it is possible to suppress inter-particle hopping at the time of voltage application. As a result, the leakage current is reduced, and the semiconductor-containing layer is less likely to cause dielectric breakdown. On the other hand, when the compounding amount of semiconductor particles is increased, the charge density of the semiconductor-containing layer can be increased. However, the flexibility and the resistance to dielectric breakdown may be reduced.
  • the compounding amount of the semiconductor particles may be appropriately determined so that the semiconductor-containing layer has desired dielectric constant, volume resistivity, flexibility, etc., in consideration of contradictory advantages.
  • the compounding amount of the semiconductor particles may be 1 part by mass or more and 120 parts by mass or less with respect to 100 parts by mass of the elastomer. It is more preferable that the amount is 5 parts by mass or more and 80 parts by mass or less.
  • the shape of the semiconductor particles is not particularly limited.
  • the aspect ratio of the semiconductor particles when the aspect ratio of the semiconductor particles is small, the semiconductor particles are less likely to be in contact with each other even if the blending amount to the elastomer is large. Therefore, it is effective to suppress inter-particle hopping at the time of voltage application.
  • the aspect ratio of the semiconductor particles when the aspect ratio of the semiconductor particles is large, the charge density may be able to be increased even if the blending amount to the elastomer is small.
  • the thickness of the dielectric layer affects the relationship between applied voltage and generated force. That is, if the thickness of the dielectric layer is reduced, the applied voltage per unit thickness can be reduced. Therefore, it is desirable that the thickness of the dielectric layer be small. That is, it is desirable that the thickness of the semiconductor-containing layer be thin.
  • the size of the semiconductor particles may be appropriately determined in accordance with the thickness of the semiconductor-containing layer. For example, when the thickness of the semiconductor-containing layer is about 20 ⁇ m, the particle diameter of the semiconductor particles (particle diameter of primary particles that are not aggregates) is preferably 500 nm or less, 100 nm or less, and further 50 nm or less It is more preferable that there be.
  • the semiconductor-containing layer may have at least one of an inorganic semiconductor and an organic semiconductor.
  • the organic semiconductor polyaniline, polythiophene or the like is preferably used. It is desirable that the semiconductor-containing layer includes particles of an inorganic semiconductor from the viewpoint of increasing the carrier concentration and preventing the entry of impurities. Further, from the viewpoint of increasing the dielectric breakdown strength of the semiconductor-containing layer, the volume resistivity of the semiconductor-containing layer is preferably 10 10 ⁇ ⁇ cm or more. 10 12 ⁇ ⁇ cm or more is preferable.
  • the semiconductor-containing layer may further include insulating particles in addition to the semiconductor. By blending the insulating particles, the volume resistivity of the semiconductor-containing layer can be increased, and the dielectric breakdown strength can be increased.
  • insulating particles for example, powders such as silica, titanium oxide, barium titanate, calcium carbonate, clay, calcined clay, and talc may be used. These may be used alone or in combination of two or more.
  • silica, titanium oxide and barium titanate those produced by a hydrolysis reaction (sol-gel method) of an organic metal compound may be used. For example, the dielectric constant of barium titanate is large.
  • the semiconductor-containing layer can contain, in addition to the insulating particles, a crosslinking agent, a reinforcing agent, a plasticizer, an antiaging agent, a coloring agent, and the like.
  • the dielectric layer includes an elastomer and a high resistance layer having a volume resistivity of 10 12 ⁇ ⁇ cm or more.
  • the high resistance layer may be formed only of an elastomer, or may be formed including an elastomer and other components.
  • ethylene-propylene-diene copolymer EPDM
  • isoprene rubber natural rubber, fluororubber, nitrile rubber (NBR), hydrogenated nitrile rubber (H-NBR)
  • silicone rubber urethane rubber, acrylic Rubber, butyl rubber, styrene butadiene rubber, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-acrylic acid ester copolymer and the like are preferable.
  • an elastomer modified by introducing a functional group may be used, such as an epoxidized natural rubber, a carboxyl group-modified hydrogenated nitrile rubber (XH-NBR), or the like.
  • XH-NBR carboxyl group-modified hydrogenated nitrile rubber
  • it can be used individually by 1 type or in mixture of 2 or more types.
  • Insulating particles may be mentioned as one of the other components to be blended in addition to the elastomer. By blending the insulating particles, the volume resistivity of the high resistance layer can be increased.
  • the insulating particles for example, powders such as silica, titanium oxide, barium titanate, calcium carbonate, clay, calcined clay, and talc may be used. These may be used alone or in combination of two or more.
  • silica, titanium oxide and barium titanate may be produced by a sol-gel method.
  • the elastomer and the insulating particles be chemically bonded in order to block the flow of electrons and to increase the insulating property.
  • both the elastomer and the insulating particles have functional groups that can react with one another.
  • the functional group include a hydroxyl group (-OH), a carboxyl group (-COOH), and a maleic anhydride group.
  • the elastomer one modified by introducing a functional group, such as a carboxyl group-modified hydrogenated nitrile rubber, is suitable.
  • insulating particles functional groups can be introduced or the number of functional groups can be increased by surface treatment according to the production method or after production. The greater the number of functional groups, the better the reactivity of the elastomer with the insulating particles.
  • the compounding amount of the insulating particles may be determined in consideration of the volume resistivity of the elastomer and the like. For example, it is desirable to be 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the elastomer. If the amount is less than 5 parts by mass, the effect of increasing the electrical resistance is small. On the other hand, if it exceeds 50 parts by mass, the high resistance layer may become hard and the flexibility may be lost.
  • the semiconductor-containing layer is obtained by, for example, applying a raw material liquid containing a raw material such as an elastomer and polymers and semiconductors onto a substrate and drying the coating (need Accordingly, they can be produced by crosslinking reaction).
  • a raw material liquid containing a raw material such as an elastomer and polymers and semiconductors
  • they can be produced by crosslinking reaction.
  • each layer is formed by applying and drying the raw material liquid on a base material (crosslinking reaction, if necessary).
  • a layered product can be manufactured by piling up the formed layers, and exfoliating a substrate.
  • the pair of electrodes includes a binder and a conductive material.
  • Resin and an elastomer can be used as a binder.
  • An elastomer is preferable as a binder from the viewpoint of forming an electrode whose electric resistance is unlikely to increase even when it is expanded and contracted.
  • the type of conductive material is not particularly limited. It may be appropriately selected from conductive carbon powders such as carbon black, carbon nanotubes and graphite, and metal powders such as silver, gold, copper, nickel, rhodium, palladium, chromium, titanium, platinum, iron, and alloys thereof. . Alternatively, a powder made of metal-coated particles, such as silver-coated copper powder, may be used. These may be used alone or in combination of two or more.
  • the particles to be coated with metal are particles other than metal
  • the specific gravity of the conductive material can be reduced as compared to the case where the particles are coated only with metal. Therefore, when it is made a paint, the sedimentation of the conductive material is suppressed, and the dispersibility is improved.
  • conductive materials of various shapes can be easily manufactured. In addition, the cost of the conductive material can be reduced.
  • metal materials such as silver listed above may be used.
  • carbon materials such as carbon black, metal oxides such as calcium carbonate, titanium dioxide, aluminum oxide and barium titanate, inorganic substances such as silica, resins such as acrylic and urethane, etc. may be used. .
  • the electrode may contain, in addition to the binder and the conductive material, if necessary, additives such as a crosslinking agent, a dispersing agent, a reinforcing agent, a plasticizer, an antiaging agent, and a coloring agent.
  • additives such as a crosslinking agent, a dispersing agent, a reinforcing agent, a plasticizer, an antiaging agent, and a coloring agent.
  • a conductive material if necessary, an additive is added to a polymer solution in which the polymer of the elastomer component is dissolved in a solvent, and the conductive paint is prepared by stirring and mixing.
  • the electrode may be formed by applying the prepared conductive paint directly to the two opposing surfaces of the dielectric layer.
  • a conductive paint may be applied to the release film to form an electrode, and the formed electrode may be transferred to the two opposing surfaces of the dielectric layer.
  • a method of applying the conductive paint various methods which are already known can be adopted. For example, in addition to printing methods such as inkjet printing, flexographic printing, gravure printing, screen printing, pad printing and lithography, dip method, spray method, bar coat method and the like can be mentioned. For example, when the printing method is adopted, it is possible to easily separate the application part and the non-application part. Also, printing of large areas, thin lines, and complicated shapes is easy. Among the printing methods, the screen printing method is preferable because a paint having a high viscosity can be used and the adjustment of the thickness of the coating film is easy.
  • FIG. 5 shows a perspective view of the speaker of this embodiment.
  • FIG. 6 is a cross-sectional view taken along the line VI-VI of FIG.
  • the speaker 4 includes a first outer frame 40a, a first inner frame 41a, a first dielectric layer 42a, a first outer electrode 43a, a first inner electrode 44a, and One diaphragm 45a, second outer frame 40b, second inner frame 41b, second dielectric layer 42b, second outer electrode 43b, second inner electrode 44b, second diaphragm 45b, eight A bolt 460, eight nuts 461, and eight spacers 462 are provided.
  • the first outer frame 40 a and the first inner frame 41 a is made of resin and has a ring shape.
  • the first dielectric layer 42a has a circular thin film shape.
  • the first dielectric layer 42a is an n-type semiconductor-containing layer containing the same nitrile rubber and n-type semiconductor inorganic particles as in the first embodiment.
  • the first dielectric layer 42a is stretched between the first outer frame 40a and the first inner frame 41a. That is, the first dielectric layer 42a is held and fixed by the first outer frame 40a on the front side and the first inner frame 41a on the back side in a state where a predetermined tension is secured.
  • the first diaphragm 45a is made of resin and has a disk shape.
  • the first diaphragm 45a has a smaller diameter than the first dielectric layer 42a.
  • the first diaphragm 45a is disposed substantially at the center of the surface of the first dielectric layer 42a.
  • the first outer electrode 43a has a ring shape.
  • the first outer electrode 43a is attached to the surface of the first dielectric layer 42a.
  • the first inner electrode 44a also has a ring shape.
  • the first inner electrode 44a is attached to the back surface of the first dielectric layer 42a.
  • the first outer electrode 43a and the first inner electrode 44a face in the front and back direction with the first dielectric layer 42a interposed therebetween.
  • Each of the first outer electrode 43a and the first inner electrode 44a contains acrylic rubber and carbon black.
  • the first outer electrode 43a includes a terminal 430a.
  • the first inner electrode 44a includes a terminal 440a. An external voltage is applied to the terminals 430a and 440a.
  • second member Configuration of second outer frame 40b, second inner frame 41b, second dielectric layer 42b, second outer electrode 43b, second inner electrode 44b, second diaphragm 45b
  • first member The material and shape are the first outer frame 40a, the first inner frame 41a, the first dielectric layer 42a, the first outer electrode 43a, the first inner electrode 44a, the first diaphragm 45a
  • first member The same applies to the structure, the material, and the shape.
  • the arrangement of the second member is symmetrical to the arrangement of the first member in the front and back direction.
  • the second dielectric layer 42b is an n-type semiconductor-containing layer and is stretched between the second outer frame 40b and the second inner frame 41b.
  • the second diaphragm 45b is disposed substantially at the center of the surface of the second dielectric layer 42b.
  • the second outer electrode 43b is printed on the surface of the second dielectric layer 42b.
  • the second inner electrode 44b is printed on the back surface of the second dielectric layer 42b.
  • Each of the second outer electrode 43 b and the second inner electrode 44 b contains acrylic rubber and carbon black. A voltage is applied from the outside to the terminal 430 b of the second outer electrode 43 b and the terminal 440 b of the second inner electrode 44 b.
  • the first member and the second member are fixed by eight bolts 460 and eight nuts 461 via eight spacers 462.
  • the sets of “bolts 460-nuts 461-spacers 462” are arranged at predetermined intervals in the circumferential direction of the speaker 4.
  • the bolt 460 penetrates from the surface of the first outer frame 40a to the surface of the second outer frame 40b.
  • the nut 461 is screwed to the through end of the bolt 460.
  • the spacer 462 is made of resin and is annularly mounted on the shaft portion of the bolt 460.
  • the spacer 462 secures a predetermined interval between the first inner frame 41a and the second inner frame 41b.
  • voltages of opposite phase are applied to the terminals 430a and 440a and the terminals 430b and 440b.
  • the offset voltage +1 V is applied to the terminals 430a and 440a
  • the thickness of the portion of the first dielectric layer 42a disposed between the first outer electrode 43a and the first inner electrode 44a is thin. Become.
  • the portion extends radially.
  • reverse phase voltage offset voltage -1 V
  • offset voltage -1 V reverse phase voltage
  • the thickness of the portion of the second dielectric layer 42b disposed between the second outer electrode 43b and the second inner electrode 44b is increased.
  • the portion shrinks in the radial direction.
  • the second dielectric layer 42b is elastically deformed by its own biasing force in the direction shown by the white arrow Y1b in FIG. 6 while pulling the first dielectric layer 42a.
  • the first dielectric layer 42 a pulls the second dielectric layer 42 b. While being elastically deformed in the direction shown by the white arrow Y1a in FIG. Thus, air is vibrated by vibrating the first diaphragm 45a and the second diaphragm 45b to generate sound.
  • the dielectric constant of the first dielectric layer 42 a and the second dielectric layer 42 b is large, and the dielectric breakdown strength is also large.
  • the effect of improving the relative dielectric constant by the polarization of the n-type semiconductor inorganic particles can be obtained.
  • the first outer electrode 43a, the first inner electrode 44a, the second outer electrode 43b, and the second inner electrode 44b are flexible and have elasticity. .
  • the entire speaker 4 is flexible, and the movements of the first dielectric layer 42a and the second dielectric layer 42b are not easily restricted by the electrodes 43a, 44a, 43b and 44b. Therefore, the speaker 4 is excellent in durability and responsiveness. In particular, the response in the high frequency region is good.
  • FIG. 7 the cross-sectional schematic diagram of the electric power generation element in this embodiment is shown.
  • (A) shows the time of expansion
  • (b) shows the time of contraction.
  • the power generation element 3 includes a dielectric layer 30, electrodes 31a and 31b, and wirings 32a to 32c.
  • the dielectric layer 30 is composed of an n-type semiconductor-containing layer containing the same nitrile rubber and n-type semiconductor inorganic particles as in the first embodiment.
  • the electrode 31 a is disposed to cover substantially the entire top surface of the dielectric layer 30.
  • the electrode 31 b is disposed so as to cover substantially the entire lower surface of the dielectric layer 30.
  • Wirings 32a and 32b are connected to the electrode 31a. That is, the electrode 31a is connected to an external load (not shown) via the wiring 32a. Further, the electrode 31a is connected to a power supply (not shown) via the wiring 32b.
  • the electrode 31 b is grounded by the wiring 32 c.
  • Each of the electrodes 31a and 31b contains acrylic rubber and carbon black.
  • the dielectric constant of the dielectric layer 30 is large, and the dielectric breakdown strength is also large.
  • the power generation element 3 can store a large amount of charge between the electrodes 31a and 31b, and is excellent in durability.
  • the electrodes 31a and 31b are flexible and stretchable. Therefore, the whole of the power generation element 3 is flexible, and the movement of the dielectric layer 30 is not easily restricted by the electrodes 31a and 31b.
  • FIG. 8 shows a top view of the capacitive sensor.
  • FIG. 9 shows a cross-sectional view taken along the line IX-IX of FIG.
  • the capacitive sensor 2 includes a dielectric layer 20, a pair of electrodes 21a and 21b, wires 22a and 22b, and cover films 23a and 23b.
  • the dielectric layer 20 has a strip shape extending in the left-right direction.
  • the thickness of the dielectric layer 20 is about 300 ⁇ m.
  • the dielectric layer 20 is formed of an n-type semiconductor-containing layer including the same nitrile rubber and n-type semiconductor inorganic particles as in the first embodiment.
  • the electrode 21a has a rectangular shape. Three electrodes 21 a are formed on the top surface of the dielectric layer 20 by screen printing. Similarly, the electrode 21b has a rectangular shape. Three electrodes 21 b are formed on the lower surface of the dielectric layer 20 so as to face the electrode 21 a with the dielectric layer 20 interposed therebetween. The electrode 21 b is screen printed on the lower surface of the dielectric layer 20. Thus, three pairs of electrodes 21a and 21b are disposed with the dielectric layer 20 interposed therebetween. The electrodes 21a, 21b contain acrylic rubber and carbon black.
  • the wiring 22 a is connected to each of the electrodes 21 a formed on the top surface of the dielectric layer 20.
  • the electrode 21a and the connector 24 are connected by the wiring 22a.
  • the wiring 22 a is formed on the top surface of the dielectric layer 20 by screen printing.
  • the wires 22 b are connected to each of the electrodes 21 b formed on the lower surface of the dielectric layer 20 (indicated by dotted lines in FIG. 8).
  • the electrode 21 b and a connector (not shown) are connected by the wiring 22 b.
  • the wiring 22 b is formed on the lower surface of the dielectric layer 20 by screen printing.
  • the wires 22a, 22b contain acrylic rubber and silver powder.
  • the cover film 23a is made of acrylic rubber, and has a strip shape extending in the left-right direction.
  • the cover film 23a covers the top surfaces of the dielectric layer 20, the electrode 21a, and the wiring 22a.
  • the cover film 23 b is made of acrylic rubber and has a strip shape extending in the left-right direction.
  • the cover film 23b covers the lower surface of the dielectric layer 20, the electrode 21b, and the wiring 22b.
  • the movement of the capacitive sensor 2 will be described.
  • the capacitive sensor 2 when the capacitive sensor 2 is pressed from above, the dielectric layer 20, the electrode 21a, and the cover film 23a are integrally bent downward.
  • the compression reduces the thickness of the dielectric layer 20.
  • the capacitance between the electrodes 21a and 21b is increased. Deformation due to compression is detected by this capacitance change.
  • the dielectric constant of the dielectric layer 20 is large, and the dielectric breakdown strength is also large. For this reason, the capacitance of the dielectric layer 20 is increased, and even a small displacement can be detected with high sensitivity. Further, the capacitive sensor 2 is excellent in durability.
  • the electrodes 21a and 21b and the wirings 22a and 22b are flexible and stretchable. Therefore, the entire capacitive sensor 2 is flexible, and the movement of the dielectric layer 20 is not easily restricted by the electrodes 21a and 21b.
  • three pairs of electrodes 21 a and 21 b facing each other with the dielectric layer 20 narrowed are formed. However, the number, size, shape, arrangement and the like of the electrodes may be appropriately determined according to the application.
  • Example 1 The semiconductor-containing layer was manufactured using n-type inorganic semiconductor powder. Phosphorus (P) -doped tin oxide (SnO 2 ) powder ("EPSP2" manufactured by Mitsubishi Materials Corp.) was used as the n-type inorganic semiconductor powder. First, a polymer of a carboxyl group-modified hydrogenated nitrile rubber (“Terban (registered trademark) XT 8889" manufactured by LANXESS Corporation) was dissolved in acetylacetone to prepare a polymer solution having a solid content concentration of 12% by mass.
  • n-type inorganic semiconductor powder was dispersed in acetylacetone to prepare a dispersion having a concentration of 12% by mass.
  • 13 parts by mass of the dispersion liquid of the inorganic semiconductor powder was mixed with 100 parts by mass of the polymer solution to prepare a mixed liquid.
  • 5 parts by mass of an acetylacetone solution (concentration: 20% by mass) of tetrakis (2-ethylhexyloxy) titanium as a crosslinking agent was added to the prepared mixture.
  • the mixed solution was applied onto a substrate, dried, and then heated at 150 ° C. for 60 minutes to produce an n-type semiconductor-containing layer.
  • the thickness of the manufactured n-type semiconductor-containing layer is about 20 ⁇ m. This n-type semiconductor-containing layer is referred to as the semiconductor-containing layer of Example 1.
  • Example 2 An n-type semiconductor-containing layer was produced in the same manner as in Example 1 except that the blending amount of the n-type inorganic semiconductor powder dispersion was changed to 52 parts by mass.
  • the n-type semiconductor-containing layer produced is referred to as the semiconductor-containing layer of Example 2.
  • Example 3 An n-type semiconductor-containing layer was produced in the same manner as in Example 2 except that barium titanate (BaTiO 3 ) powder was added as the insulating particles in addition to the n-type inorganic semiconductor powder.
  • Barium titanate powder was manufactured as follows. First, 0.019 mol of each of diethoxy barium and tetraisopropyl titanium was dissolved in 116 ml of 2-methoxyethanol. The solution was then treated at reflux for 3 hours at 125 ° C. and then at 70 ° C. for 6 hours with reflux. The barium titanate powder thus obtained was added to a mixture of a polymer solution and a dispersion of an inorganic semiconductor powder. The n-type semiconductor-containing layer produced is referred to as the semiconductor-containing layer of Example 3.
  • Example 4 An n-type semiconductor-containing layer was produced in the same manner as in Example 1 except that the blending amount of the n-type inorganic semiconductor powder dispersion was changed to 100 parts by mass.
  • the n-type semiconductor-containing layer produced is referred to as the semiconductor-containing layer of Example 4.
  • the semiconductor-containing layer was manufactured using n-type inorganic semiconductor powder.
  • n-type inorganic semiconductor powder inorganic semiconductor powder (“ET 300 W” manufactured by Ishihara Sangyo Co., Ltd.) composed of tin oxide (SnO 2 ) doped with antimony (Sb) and titanium oxide (TiO 2 ) was used.
  • a polymer of carboxyl group-modified hydrogenated nitrile rubber (“XER32" manufactured by JSR Corporation) was dissolved in acetylacetone to prepare a polymer solution having a solid content concentration of 12% by mass.
  • n-type inorganic semiconductor powder was dispersed in acetylacetone to prepare a dispersion having a concentration of 12% by mass.
  • 50 parts by mass of the dispersion liquid of the inorganic semiconductor powder was mixed with 100 parts by mass of the polymer solution to prepare a mixed liquid.
  • 5 parts by mass of an acetylacetone solution (concentration: 20% by mass) of tetrakis (2-ethylhexyloxy) titanium as a crosslinking agent was added to the prepared mixture.
  • the mixed solution was applied onto a substrate, dried, and then heated at 150 ° C. for 60 minutes to produce an n-type semiconductor-containing layer.
  • the thickness of the manufactured n-type semiconductor-containing layer is about 20 ⁇ m. This n-type semiconductor-containing layer is referred to as the semiconductor-containing layer of Example 5.
  • Example 6 An n-type semiconductor-containing layer was produced in the same manner as in Example 1 except that the type and blending amount of the n-type inorganic semiconductor powder were changed. That is, a barium titanate (BaTiO 3 ) powder doped with lanthanum (La) manufactured as follows was used as the n-type inorganic semiconductor powder, and the compounding amount of the dispersion liquid was 60 parts by mass.
  • the n-type semiconductor-containing layer produced is referred to as the semiconductor-containing layer of Example 5.
  • diethoxybarium, tetraisopropyltitanium, and triisopropoxy lanthanum were dissolved in 116 ml of 2-methoxyethanol at a molar ratio of 0.995: 1: 0.005 with 0.019 mol of diethoxybarium.
  • the solution was then treated at reflux for 3 hours at 125 ° C. and then at 70 ° C. for 6 hours with reflux. In this way, barium titanate powder doped with 0.5 mol% of lanthanum was obtained.
  • Example 7 Example 6 and Example 6 were repeated except that in the preparation of the lanthanum-doped barium titanate powder, the compounding ratio of diethoxybarium, tetraisopropyltitanium, and triisopropoxylanthanum was changed to 0.90: 1: 0.1. Similarly, an n-type semiconductor-containing layer was manufactured. The doped amount of lanthanum in the obtained barium titanate powder is 10 mol%. The n-type semiconductor-containing layer produced is referred to as the semiconductor-containing layer of Example 7.
  • Example 8 An n-type semiconductor-containing layer was produced in the same manner as in Example 7 except that no crosslinking agent was added. The produced n-type semiconductor-containing layer is referred to as the semiconductor-containing layer of Example 8.
  • Example 9 An n-type semiconductor-containing layer was produced in the same manner as in Example 1 except that the type and blending amount of the n-type inorganic semiconductor powder were changed. That is, as the n-type inorganic semiconductor powder, niobium (Nb) -doped barium titanate (BaTiO 3 ) powder manufactured as follows was used, and the blending amount of the dispersion liquid was 60 parts by mass. The n-type semiconductor-containing layer produced is referred to as the semiconductor-containing layer of Example 9.
  • diethoxybarium, tetraisopropyltitanium and pentaethoxyniobium were dissolved in 116 ml of 2-methoxyethanol at a molar ratio of 0.95: 1: 0.05 and 0.019 mole of diethoxybarium.
  • the solution was then treated at reflux for 3 hours at 125 ° C. and then at 70 ° C. for 6 hours with reflux.
  • a barium titanate powder doped with 5 mol% of niobium was obtained.
  • Example 10 In the preparation of the niobium-doped barium titanate powder in Example 9, niobium-doped titanium dioxide was prepared using only tetraisopropyl titanium and pentaethoxy niobium and changing the compounding ratio of the two to 0.95: 0.05. A (TiO 2 ) powder was produced. Then, an n-type semiconductor-containing layer was manufactured in the same manner as in Example 9 except that this powder was used. The doped amount of niobium in the obtained titanium dioxide powder is 5 mol%. The n-type semiconductor-containing layer produced is referred to as the semiconductor-containing layer of Example 10.
  • Example 11 The semiconductor-containing layer was manufactured using p-type organic semiconductor polyaniline instead of n-type inorganic semiconductor powder.
  • 1 mol (107 g) of o-toluidine was added to 1000 ml of 1N hydrochloric acid to prepare an o-toluidine solution.
  • 1 mol (228.21 g) of ammonium persulfate dissolved in 500 ml of 1 N hydrochloric acid is added as an oxidizing agent, and a polymerization reaction is carried out by stirring at 15 ° C. for 10 hours. I got toluidine.
  • the obtained poly o-toluidine was washed with methanol and water, and then added to 0.1 N sodium hydroxide solution to carry out a dedoping reaction.
  • the de-doped poly o-toluidine was again washed with methanol and water and dissolved in tetrahydrofuran (THF).
  • THF tetrahydrofuran
  • a polyester urethane resin having a sulfonic acid sodium group (“Vylon (registered trademark) UR-5537" manufactured by Toyobo Co., Ltd.) was dissolved in THF to prepare a polymer solution.
  • a polymer solution was mixed with a THF solution of poly o-toluidine to prepare a mixture.
  • volume resistivity The volume resistivity of the semiconductor-containing layer was measured according to JIS K6271 (2008). The measurement was performed by applying a DC voltage of 100V.
  • Elastic modulus The static shear modulus of the semiconductor-containing layer was measured according to JIS K 6254 (2003). The elongation percentage in the low deformation tensile test was 25%.
  • Electrostrictive actuators were manufactured using each of the semiconductor-containing layers of Examples 1 to 11 as a dielectric layer.
  • the electrodes were formed by screen printing conductive paint on both the front and back sides of the dielectric layer.
  • the conductive paint was prepared by mixing and dispersing carbon black in an acrylic rubber polymer solution. Then, the generated force, the amount of displacement, and the dielectric breakdown strength of the manufactured actuators of Examples 1 to 11 were measured.
  • the actuators of Examples 1 to 11 are included in the flexible transducer of the present invention.
  • the dielectric layer was manufactured as follows. First, a polymer of carboxyl group-modified hydrogenated nitrile rubber ("Terban XT 8889" manufactured by LANXESS Corporation) was dissolved in acetylacetone to prepare a polymer solution having a solid content concentration of 12% by mass. Next, 5 parts by mass of a crosslinking agent tetrakis (2-ethylhexyloxy) titanium in acetylacetone solution (concentration 20 mass%) was mixed with 100 parts by mass of the polymer solution. Then, the mixed solution was applied onto a substrate, dried, and then heated at 150 ° C. for 60 minutes to produce a dielectric layer.
  • the manufactured dielectric layer is referred to as the dielectric layer of Comparative Example 1
  • the actuator including the dielectric layer is referred to as the actuator of Comparative Example 1.
  • Comparative Example 2 TiO 2 powder (Sigma Aldrich, average particle size 100 nm) as insulating particles except that blended were prepared similarly to the dielectric layer of the Comparative Example 1.
  • the manufactured dielectric layer is referred to as the dielectric layer of Comparative Example 2
  • the actuator including the dielectric layer is referred to as the actuator of Comparative Example 2.
  • Comparative Example 3 SiO 2 powder (Sigma Aldrich, average particle size 100 nm) as insulating particles except that blended were prepared similarly to the dielectric layer of the Comparative Example 1.
  • the manufactured dielectric layer is referred to as the dielectric layer of Comparative Example 3
  • the actuator including the dielectric layer is referred to as the actuator of Comparative Example 3.
  • Comparative Example 4 First, in the same manner as Comparative Example 1, a nitrile rubber film was produced from a polymer (the same as above) of a carboxyl group-modified hydrogenated nitrile rubber. Next, the nitrile rubber film was immersed in a LiClO 4 / propylene carbonate electrolyte for 24 hours to allow the ion component (LiClO 4 ) of the electrolyte to permeate into the nitrile rubber film. Then, it was made to dry at normal temperature in a vacuum oven for 24 hours. Thus, the nitrile rubber film impregnated with the ion component was manufactured and used as a dielectric layer. The manufactured dielectric layer is referred to as the dielectric layer of Comparative Example 4, and the actuator including the dielectric layer is referred to as the actuator of Comparative Example 4.
  • FIG. 10 shows a front side front view of the actuator attached to the measuring device.
  • FIG. 11 is a cross-sectional view taken along the line VI-VI of FIG.
  • the upper end of the actuator 5 is gripped by the upper chuck 52 in the measuring device.
  • the lower end of the actuator 5 is gripped by the lower chuck 53.
  • the actuator 5 is attached between the upper chuck 52 and the lower chuck 53 in a state of being stretched in the vertical direction in advance (stretching ratio 25%).
  • a load cell (not shown) is disposed above the upper chuck 52.
  • the actuator 5 comprises a dielectric layer 50 and a pair of electrodes 51a and 51b.
  • the dielectric layer 50 has a rectangular plate shape of 50 mm long and 25 mm wide in a natural state.
  • the configuration of the dielectric layer 50 is different for each actuator (see Table 1 below).
  • the electrodes 51 a and 51 b are disposed to face each other in the front and back direction with the dielectric layer 50 interposed therebetween.
  • the electrodes 51a and 51b each have a rectangular plate shape of 40 mm long, 25 mm wide, and about 10 ⁇ m thick in a natural state.
  • the electrodes 51a and 51b are arranged in a state of being offset by 10 mm in the vertical direction.
  • the electrodes 51 a and 51 b overlap each other in the range of 30 mm long and 25 mm wide via the dielectric layer 50.
  • a wire (not shown) is connected to the lower end of the electrode 51a.
  • a wire (not shown) is connected to the upper end of the electrode 51b.
  • the electrodes 51a and 51b are connected to a power supply (not shown) via the respective wirings.
  • the electrode 51a on the front side is a positive electrode
  • the electrode 51b on the rear side is a negative electrode.
  • the measurement of the dielectric breakdown strength was performed by stepwise increasing the voltage applied between the electrodes 51a and 51b until the dielectric layer 50 was destroyed. Then, a value obtained by dividing the voltage value just before the dielectric layer 50 is broken by the entire thickness of the dielectric layer 50 is taken as the dielectric breakdown strength.
  • the measurement of the generated force was performed using the same apparatus as the measurement of the dielectric breakdown strength (see FIGS. 10 and 11).
  • a voltage is applied between the electrodes 51a and 51b, an electrostatic attractive force is generated between the electrodes 51a and 51b to compress the dielectric layer 50.
  • the stretching of the dielectric layer 50 reduces the stretching force in the vertical direction.
  • the stretching force decreased at the time of voltage application was measured by a load cell and used as the generated force.
  • the generated force was measured at an electric field strength of 30 V / ⁇ m.
  • the maximum voltage of the dielectric layer 50 was measured by increasing the applied voltage stepwise until the dielectric layer 50 was destroyed.
  • FIG. 13 shows a cross-sectional view taken along line XIII-XIII in FIG.
  • the actuator 6 consists of the dielectric layer 60 and a pair of electrode 61a, 61b.
  • the dielectric layer 60 is in the form of a circular thin film having a diameter of 70 mm.
  • the dielectric layer 60 is disposed in a biaxially stretched state by 25%.
  • the configuration of the dielectric layer 60 is different for each actuator (see Table 1 below).
  • the pair of electrodes 61 a and 61 b are arranged to face each other in the vertical direction with the dielectric layer 60 interposed therebetween.
  • the electrodes 61a and 61b are in the form of a circular thin film having a diameter of about 27 mm, and are arranged substantially concentrically with the dielectric layer 60. At the outer peripheral edge of the electrode 61a, a terminal portion 610a that protrudes in the radial direction is formed. The terminal portion 610a has a rectangular plate shape. Similarly, at the outer peripheral edge of the electrode 61b, a terminal portion 610b that protrudes in the radial direction is formed. The terminal portion 610b has a rectangular plate shape. The terminal portion 610 b is disposed at a position facing the terminal portion 610 a by 180 °. The terminal portions 610a and 610b are each connected to the power supply 62 via a conductor.
  • a marker 630 is attached to the electrode 61a in advance. The displacement of the marker 630 was measured by the displacement meter 63, and was used as the displacement amount of the actuator 6. The displacement was measured at an electric field strength of 30 V / ⁇ m. Also, the applied voltage was increased stepwise until the dielectric layer 60 was destroyed, and the maximum displacement of the dielectric layer 60 was measured.
  • Displacement rate (%) (displacement amount / radius of electrode) ⁇ 100 (1)
  • Table 1 summarizes the composition and physical properties of the dielectric layer in each actuator of the example, and the measurement results of the force generated by the actuator, the displacement amount, and the dielectric breakdown strength.
  • Table 2 summarizes the composition and physical properties of the dielectric layer in each actuator of the comparative example, and the measurement results of the force generated by the actuator, the displacement amount, and the dielectric breakdown strength.
  • the dielectric breakdown strength is higher than that of the actuator of the second embodiment.
  • the compounding amount of the inorganic semiconductor powder is large.
  • the dielectric constant is larger than that of the dielectric layers of Examples 1 to 3
  • the volume resistivity becomes equal or smaller. Therefore, although the dielectric breakdown strength of the actuator of Example 4 was lower than that of the actuators of Examples 1 to 3, the generated force per unit electric field strength (generated force / breakdown strength) was increased.
  • the compounding amounts of the semiconductor and the insulating particles may be appropriately determined in accordance with the dielectric breakdown strength and generation force required for each application.
  • Example 11 In the dielectric layer (semiconductor-containing layer) of Example 11 in which the p-type organic semiconductor is used, the relative dielectric constant is increased but the volume resistivity is decreased as compared with the dielectric layer of Comparative Example 1. . However, the generated force and the dielectric breakdown strength of the actuator of Example 11 were larger than that of the actuator of Comparative Example 1.
  • the flexible transducer of the present invention can be widely used as an actuator for converting mechanical energy to electrical energy, a sensor, a power generating element, etc., or a speaker for converting acoustic energy to electrical energy, a microphone, a noise canceler, etc. .
  • it is suitable as an artificial muscle used for industry, medicine, welfare robot, assist suit, etc., a small pump for cooling electronic parts, for medical use, etc., and a flexible actuator used for medical instruments etc.

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  • Engineering & Computer Science (AREA)
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  • Acoustics & Sound (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

La présente invention concerne un transducteur souple (1) pourvu : d'une couche diélectrique (10) comportant une couche (12), qui contient un semi-conducteur et qui contient un élastomère, et un semi-conducteur inorganique et/ou un semi-conducteur organique ; et d'une paire d'électrodes (11a, 11b), qui sont disposées avec la couche diélectrique (10) entre elles, et qui contiennent un liant et un matériau conducteur. La couche (12) qui contient un semi-conducteur possède une constante diélectrique élevée, et de bonnes caractéristiques isolantes. Par conséquent, grâce au transducteur souple (1), une sortie importante peut être obtenue en appliquant une forte tension entre les électrodes (11a, 11b).
PCT/JP2013/083911 2013-01-30 2013-12-18 Transducteur souple WO2014119166A1 (fr)

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JP2014528747A JP5633769B1 (ja) 2013-01-30 2013-12-18 柔軟なトランスデューサ
US14/674,231 US20150202656A1 (en) 2013-01-30 2015-03-31 Flexible transducer

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JP2013-015193 2013-01-30
JP2013015193 2013-01-30

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CN104816315A (zh) * 2015-03-18 2015-08-05 苏州市恒加新精密机械科技有限公司 一种纤维收缩控制的仿生机械手臂
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